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Research Article

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Tunable KIT-6 Mesoporous Sulfonic Acid Catalysts for Fatty Acid


Esterication
Cyril Pirez, Jean-Michel Caderon, Jean-Philippe Dacquin, Adam F. Lee, and Karen Wilson*
Cardi Catalysis Institute, School of Chemistry, Cardi University, Park Place, Cardi CF10 3AT, U.K.

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Publication Date (Web): July 9, 2012 | doi: 10.1021/cs300161a

S Supporting Information
*

ABSTRACT: We report the rst catalytic application of pore-expanded KIT-6


propylsulfonic acid (PrSO3H) silicas, in fatty acid esterication with methanol
under mild conditions. As-synthesized PrSO3H-KIT-6 exhibits a 40 and 70%
enhancement in turnover frequency (TOF) toward propanoic and hexanoic acid
esterication, respectively, over a PrSO3H-SBA-15 analogue of similar 5 nm pore
diameter, reecting the improved mesopore interconnectivity of KIT-6 over SBA15. However, pore accessibility becomes rate-limiting in the esterication of
longer chain lauric and palmitic acids over both solid acid catalysts. This problem
can be overcome via hydrothermal aging protocols which permit expansion of the
KIT-6 mesopore to 7 nm, thereby doubling the TOF for lauric and palmitic acid
esterication over that achievable with PrSO3H-SBA-15.
KEYWORDS: biodiesel, nanostructured silicas, green chemistry, solid acids, esterication
solid acid catalysts, including SO4/ZrO2,1214 Cs-exchanged
heteropolyacids,1519 tungstated zirconia,20 zirconium phosphate2123 and Naon/SiO2 composite (SAC-13).24 Poor
mass-transport in these systems has focused recent attention
on mesporous solid acids,25 with SBA-15 derived catalysts
proving popular candidates for biodiesel synthesis. Indeed,
SBA-15 supported propylsulfonic and arylsufonic acids exhibit
promising activity in FFA esterication2630 and in the
esterication of shorter chain acids pertinent to pyrolysis oil
pretreatment31 wherein high acid contents hinder rening.
We recently demonstrated that macropore incorporation32
into mesoporous SBA-15 sulfonic acids, or swelling of SBA-15
mesopores,33 signicantly enhances activity toward both FFA
esterication and triglyceride transesterication. In the case of
macro-mesoporous SBA-15, inclusion of 300 nm macropores
fractures the micrometer-long, parallel mesopore channels
normally present within SBA-15, promoting in-pore molecular
diusion and active site accessibility. Improving pore
interconnectivity, for example, through the Ia3d pore
architecture of KIT-6,34 could provide another means to
enhance pore accessibility (Scheme 1). KIT-6 mesoporous
materials exhibit improved characteristics for biomolecule
immobilization (e.g., enzymes),35 related to better diusion
within the interconnected cubic structure. Interconnected silica
supports also signicantly enhance the per-site activity of Pd
nanoparticles in allylic alcohol selective oxidation, wherein Pd/
KIT-6 is far superior to Pd/SBA-15.36 We therefore
hypothesized that sulfonic acid functionalization of KIT-6,
and expanded variants thereof, may oer tailored solid acid

1. INTRODUCTION
Concerns over dwindling fossil fuel reserves, coupled with
rising atmospheric CO2 emissions, is helping to drive the
renewable energy revolution and the associated promise of
lower greenhouse gas emissions. Wind, solar, and tidal energy
resources are all potential alternatives for stationary power
generation;1 however, liquid biofuels are one of the few
competitors to petroleum able to contribute to transportation
needs, with 9% of the transportation fuel market predicted to
be met through biofuels by 2030.2
Biodiesel, comprising fatty acid methyl esters (FAMEs)3
produced via the transesterication of triacyl glycerides from
nonfood oil sources, is an attractive and (potentially)
sustainable means to reduce current fossil fuel dependency,
and is seeing a renaissance following steeply rising petroleum
costs. However, current industrial biodiesel production is
neither energy ecient nor environmentally friendly.4 Although
the commercial homogeneous base catalysts employed, Na or K
methoxide, are very active for such transesterication, the strict
guidelines on residual alkali content in biofuel at <5 ppm,5,6
necessitate thorough aqueous quench and neutralization steps,
with associated soap formation making biodiesel separation
energy intensive.7 Furthermore, plant, algal, and waste oil
feedstock pretreatments are essential to remove free fatty acid
(FFA) impurities,8 which are also strictly regulated in biodiesel,
and can neutralize soluble base catalysts resulting in soap
formation. New heterogeneous catalysts are thus required at
various stages in biodiesel production to improve energy
eciency, and permit facile catalyst separation and continuous
process operation.9
Esterication is widely used to remove FFAs,10 which are
particularly prevalent in waste oils and grease (up to 10
33%).11 Fatty acid esterication has been studied over many
2012 American Chemical Society

Received: March 9, 2012


Revised: June 20, 2012
Published: June 21, 2012
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Research Article

stirring at room temperature for 24 h. The sulfonated solid


product was subsequently ltered, washed three times with
methanol, and dried at 80 C. Materials were stored in air and
used without further modication.
Catalyst Characterization. Textural and structural properties were measured by a combination of N2 porosimetry,
transmission electron microscopy (TEM), and X-ray diraction
(XRD), with pre- and postoxidation sulfur content determined
by thermogravimetric analysis (TGA, bulk) and X-ray photoelectron spectroscopy (XPS, surface), with acid site titrations
performed by NH3 pulse chemisorption.
Nitrogen porosimetry was undertaken on a Quantachrome
Nova 1200 porosimeter, with samples degassed at 120 C for 2
h prior recording adsorption/desorption isotherms. Brunauer
EmmettTeller (BET) surface areas were calculated over the
relative pressure range 0.010.2, while pore diameters were
calculated by applying the BarrettJoynerHalenda (BJH)
method to the desorption branch of the isotherm. Low angle
XRD patterns were recorded on a PANalytical XpertPro
diractometer tted with an Xcelerator detector and Cu K
(1.54 ) source. Low angle diraction peaks were recorded
over the range 2 = 0.38 with a step size of 0.01 and
calibrated against a Si standard. TEM images were viewed with
a Phillips CM12 transmission electron microscope operating at
100 kV. Images recorded by a SIS MegaView III digital camera,
with the data analyzed using ImageJ software. Scanning electron
microscopy-energy dispersive X-ray (SEM/EDX) was performed with a Carl Zeiss Evo-40 instrument, with samples
mounted on conductive carbon tape. XPS was performed on a
Kratos Axis HSi instrument tted with a charge neutralizer and
magnetic focusing lens employing Al K monochromated
radiation (1486.7 eV). Spectral tting was performed using
CasaXPS version 2.3.14, with binding energies corrected to the
C 1s peak at 284.5 eV, with S 2p XP spectra tted using a
common Gaussian/Lorentzian peak shape. Errors were
estimated by varying the Shirley background-subtraction
procedure across reasonable limits and recalculating the
component ts. TGA was performed using a Stanton Redcroft
STA780 thermal analyzer at 10 C.min1 under owing He (20
mL min1 total) for hydroxyl group density and sulfonic acid
decomposition studies respectively.
Acid site titration was performed on a Quantachrome
CHEMBET-3000 instrument by pulse chemisorption, using
pure NH3 (BOC 99.98%). 50 mg of catalyst was outgassed at
150 C for 2 h under owing He, after which NH3 adsorption
was performed at 100 C to prevent NH3 physisorption on the
silica surface. Titration was performed by injecting 500 L
pulses of NH3 with a gas syringe until the detector signal in
both TCD and mass spectrometer reached a plateau, indicating
that the acid sites were saturated.
Catalytic Esterication. Esterication was performed
under stirred batch conditions at atmospheric pressure in a
Radleys carousel reaction station using 25 mm diameter glass
reactor vessels. Reactions were conducted using 10 mmol
propanoic, hexanoic, lauric, or palmitic acid at 60 C in 12.5 mL
of methanol (molar ratio nMeOH/nacid = 30 under which
conditions the organic acid and methanol were completely
miscible) with 50 mg of catalyst and 0.59 mL of dihexylether as
an internal standard. Reaction proles were obtained via
periodic sampling and o-line GC analysis, with product
calibration curves used to verify mass balances (all >98%). C3
and C6 acid esterication was monitored using a Varian 450GC equipped with a CP-Sil 5 CB 15 m 0.25 mm 0.25 m

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Publication Date (Web): July 9, 2012 | doi: 10.1021/cs300161a

Scheme 1. Diagram of (a) SBA-15 and (b) KIT-6 Unit Cells

catalysts for the diusion of bulky FFA molecules during


esterication pretreatments employed in biodiesel production.
While pore-expanded KIT-6 materials have been previously
synthesized,37 they have never been exploited in heterogeneous
catalysis. Surface grafting and oxidation of mercaptopropyl
trimethoxysilane to propylsulfonic acid (PrSO3H) was selected
as a means to conformally functionalize the dierent silica pore
architectures to introduce acidic groups without the risk of pore
blockage or leaching of the grafted component. Here we report
on the rst synthesis and application of PrSO3H-KIT-6
materials with tunable pore diameters, and compare their
performance in C3-16 organic acid esterication against a
conventional PrSO3H-SBA-15 catalyst, to identify the impact of
pore interconnectivity and diameter.

2. EXPERIMENTAL SECTION
Catalyst Preparation. SBA-15 and KIT-6 materials were
prepared following the methods of Zhao et al.38 and Ryoo et
al.,39 respectively. SBA-15 was prepared using 1.0 g of Pluronic
P123 triblock copolymer (Aldrich), which was dissolved in 7.5
mL of water and 25 mL of 2 M HCl solution (Fisher) while
stirring at 35 C. A 2.3 mL portion of TEOS (tetraethoxyorthosilane - Aldrich 99%) was then added to the solution,
which was maintained at 35 C for 24 h while stirring. The
mixture was then aged statically at 80 C for a further 24 h in a
closed propylene bottle after which the solid product ltered,
washed 3 times with deionized water, and calcined in air at 550
C for 6 h. For the synthesis of the parent KIT-6 materials 4 g
of Pluronic P123 (Aldrich) was dissolved in 144 g of distilled
water containing 7.5 g of a solution of 36% HCl. Once a
homogeneous solution was formed, 4 g of butanol was added
under stirring at 35 C. After 1 h, 8.6 g of TEOS was added at
35 C such that a molar ratio of components of 0.017 P123:1
TEOS:1.31BuOH:1.83 HCl:195 H2O was employed. The
mixture was then stirred for 24 h at 35 C, and subsequently
aged for a further 24 h at 80, 100, or 120 C under static
conditions in a closed propylene bottle to vary the mesopore
dimensions. Finally the solid product obtained was ltered and
dried at 100 C for 12 h after which the template was removed
by calcination at 550 C for 6 h.
After calcination, silicas were functionalized with sulfonic
acid groups by postgrafting, in which 1 g of KIT-6 (or SBA-15)
was added to a solution containing 1 mL of mercaptopropyl
trimethoxysilane (MPTS 95%, Alfa Aesar) in 30 mL of toluene
(Fisher 99%). The suspension was then reuxed at 130 C
under stirring for 24 h, after which the resulting thiolfunctionalized solid was ltered, washed three times with
methanol (Fisher 99%) and dried at 80 C overnight. Thiol
groups were converted into SO3H by mild oxidation with 30
mL of 30% hydrogen peroxide (Sigma-Aldrich) by continuous
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capillary column. C12 and C16 acid esterication was followed


using a Varian 450-GC equipped with a 1079 programmable
direct on-column injector and Phenomenex capillary column
ZB-1HT Inferno 15 m 0.53 mm 0.15 m wide bore
column. Dichloromethane was used as solvent to dilute the
samples for GC analysis. All catalytic proles are an average of
two separate runs with 3 injections per sample. Turnover
frequencies (TOF) were determined from the linear portion of
the initial reaction rate prole for conversions below 25%,
which were normalized to the acid site concentration
determined from NH3 titrations. Leaching studies were
performed by hot ltration methods with the reaction stopped
and the catalyst removed by ltration at 2 h, after which the
reactants were reheated and further conversion monitored for
an additional 6 h. For benchmarking catalyst activity is also
compared against a commercial Amberlyst 15 hydrogen form
(Fluka) strongly acidic macro-reticular resin with particle size
600850 m and acid site loading 4.7 mmol/g.

Figure 2. Powder XRD patterns of parent SBA-15 and KIT-6


mesoporous silicas.

3. RESULTS AND DISCUSSION


Materials Characterization. Successful synthesis of SBA15 and pore-expanded KIT-6 parent silicas was conrmed by
XRD, TEM, and porosimetry. Figure 1 shows the correspond-

an increase in the unit cell parameter, and corresponding pore


spacing. The unit cell of SBA-15 is expected to be around half
that of KIT-6, consistent with our measurements summarized
in Table 1 along with those from porosimetry. The SBA-15
benchmark support has a specic area of 862 m2 g1,
signicantly higher than that of our conventional KIT-6
material aged at 80 C; however, they possess similar BJH
pore diameters of 4.9 and 5.2 nm respectively. Hydrothermal
aging of KIT-6 at 100 and 120 C expands the pore diameter
from 5.2 to 7 nm, while decreasing wall thickness, in line with
literature predictions.41,42 To date, increasing the hydrothermal
aging temperature/time has proven the only method to
increase KIT-6 pore size; attempts to use porogens such as
trimethylbenzene as a micelle expander have only resulted in
amorphous materials.37
Sulfonic acid derivatized PrSO3H-KIT-6 and PrSO3H-SBA15 materials were subsequently prepared via grafting of MPTS
and oxidation with H2O2. This is the rst report of PrSO3HKIT-6; hence the support stability postgrafting was veried by
XRD, porosimetry, and HRTEM to ensure the cubic structure
was retained (Figure 3 and Supporting Information, Figures
S1S2). HRTEM shown in Figure 4 conrms the cubic
architecture of KIT-6 silicas is retained both upon expansion
and grafting of sulfonic acid groups. The conformal nature of
this surface modication method is further evidenced by the
textural analysis in Table 2, which shows only a slight decrease
in surface area following grafting of sulfonic acid groups.
Sulfur 2p XP spectra (Figure 5) only exhibit a single doublet
centered at 169 eV, indicative of complete oxidation of the
grafted thiol groups to sulfonic acid, which is also consistent
with TGA measurements that show a single decomposition
step 450 C characteristic of propylsulfonic acid group
decomposition.43 Comparison of the bulk and surface S
contents demonstrates a higher sulfonic acid loading is achieved
on SBA-15 than across the KIT-6 family, suggesting a higher
density of reactive silanol groups in the former, which may
reect their dierent aging conditions and surface roughness.
TGA analysis (Supporting Information, Figure S4) was used to
estimate the surface hydroxyl loadings of the as-prepared
silica,44 which yields values 3.3 and 2.2 mmol g1 for SBA-15
and KIT-6-80, respectively. While this assumes the weight loss
in this temperature range 200400 C is entirely due to 2 Si
OH SiOSi + H2O, the values obtained broadly support

Figure 1. Main: pore size distributions of parent SBA-15 and KIT-6


mesoporous silicas. Inset: associated N2 adsorptiondesorption
isotherms (oset for clarity).

ing N2 isotherms and BJH pore size distributions, which reveal


all silicas exhibit Type IV isotherms with H1 hysteresis loops40
characteristic of open cylindrical pores (Figure 1 inset). BJH
analysis on the desorption branch of the isotherm conrms they
all possess well-dened mesopore diameters, which increase
with KIT-6 hydrothermal aging temperature from 80 to 120 C.
It should be noted that the hysteresis loop for KIT-6 is
narrower than that of SBA-15, which has been attributed to the
inuence of mesopore interconnectivity on N2 vaporization.40
This dierent hysteresis behavior is thus a characteristic of their
2D hexagonal (SBA-15) versus 3D cubic (KIT-6) structures.
HRTEM and XRD were used to conrm the gyroidal cubic
Ia3d and p6mm hexagonal structures (Scheme 1) and typical
lattice parameters of KIT-6 and SBA-15 respectively. Low angle
XRD in Figure 2 shows the characteristic d100, d110, and d200
planes typical of the 2D hexagonal structure in SBA-15, and the
d112 plane of the 3D gyroidal KIT-6. The d112 reection shifts to
lower angle with increasing aging temperature, consistent with
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Table 1. Structural Parameters for Parent KIT-6 and SBA-15 Supports


catalyst

surface areaa/
m2 g1

pore volume/
cm3 g1

BJH pore diameterb/


nm

plane spacingc/
nm

unit cell parameterd/


nm

wall thicknesse/
nm

TEM pore spacing/


nm

KIT-6-80
KIT-6-100
KIT-6-120
SBA-15

601
661
676
862

0.83
1.23
1.29
0.77

5.2
6.2
7.0
4.9

8.65
9.5
9.7
9.20

21.2
23.2
23.7
10.7

5.4
5.4
4.9
6.1

7.9
8.3
9.1
8.2

From BET. bAnalyzed from the desorption branch. cFrom Braggs law assuming that the peak corresponds to the (100) plane for SBA-15 and (211)
plane for KIT-6. dFor SBA-15 = a0 = (2d100)/3; for KIT-6 = (d211) 6; eFor SBA-15 = (a - pore diameter); for KIT-6 = (a/2 - pore diameter)
based on unit cell.

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length, electronic properties are not believed to signicantly


evolve; hence, subsequent variations in rate are attributed to
steric or mixing eects, the former predicted via the Taft
equation. Previous groups have shown a linear correlation
between Taft parameter and rates for C2C8 acids;46,45
however >C8 the Taft parameter remains constant.47 Steric
and bulk mixing eects are expected to be more signicant for
longer chains, wherein conformational changes are likely to
minimize the interfacial energy between the hydrophobic alkyl
chain and polar methanol solvent. For homogeneous catalysts,
the impact of such a change in fatty acid bulkiness may be
negligible; however, for a nanoporous catalyst it seems probable
that it would alter in-pore diusion, leading to the poor
performance of PrSO3H-KIT-6-80.
The eect of interconnectivity and pore expansion on
catalyst performance was assessed by comparing the PrSO3HKIT-6 family with PrSO3H-SBA-15 and a commercial macroreticular Amberlyst-15 solid acid catalyst in Figure 7. The rst
striking observation is that while higher overall conversions are
possible with Amberlyst because of its higher acid site loading
(Supporting Information, Figure S9a), both SBA-15 and KIT-6
sulfonic acid silicas signicantly outperform Amberlyst in terms
of per site activity, reecting the low porosity and accessibility
of acid sites within the polymeric catalyst. PrSO3H-KIT-6-80
also outperforms PrSO 3H-SBA-15 in C3 and C 6 acid
esterication, despite their similar pore diameters, suggesting
the improved pore interconnectivity of the former enhances
reactant/product diusion. Although these values are substantially lower than those reported for H2SO4 catalyzed propanoic
acid and hexanoic acid esterication at 60 C of 727 h1 and
478.8 h1, respectively, a similar 30% decrease in TOF is
observed between the C3 and C6 acids in these homogeneously
catalyzed systems, hinting that solution phase properties play an
important part in controlling our reaction kinetics. Corresponding values of 285 h1 and 133 h1 are reported for SAC-13
catalyzed C3 and C6 organic acid esterication,45 slightly higher
than those reported here for our PrSO3H-KIT-6 and PrSO3HSBA-15 catalysts reecting the stronger acidity of SAC-13: NH3
calorimetry gives adsorption enthalpies of 158 kJ mol1 and
130 kJ mol1 respectively for Naon and PrSO3H-SBA-15.48
The impact of acid strength on acetic acid esterication has
been demonstrated by comparing the rates for homogeneous
propane sulfonic acid (264 h1) versus H2SO4 (1365 h1)
catalysts.49 Likewise, the reported TOF for acetic acid
esterication with methanol of 436 h1 over SAC-13 is higher
than the 180 h1 for PrSO3H-SBA-15, with both slower than
homogeneous routes. Although acid strength clearly inuences
esterication activity,50 our best PrSO3H-KIT-6-120 solid acid
measures up favorably against its liquid phase propyl-sulfonic
acid analogue. Subsequent leaching tests via hot-ltration
shown in Supporting Information, Figure S9 for hexanoic acid

Figure 3. Powder XRD patterns for the sulfonic acid derivatized SBA15 and KIT-6 mesoporous silicas.

the hypothesis that the hydroxyl density in SBA-15 > KIT-6.


Acid site densities from NH3 pulse chemisorption (Table 2)
mirror the trends in bulk and surface S loadings observed by
TGA and XPS, and are typical of grafted sulfonic acid silicas
which range between 0.1 and 1 mmol g1.26
Catalytic Esterication. Sulfonic-acid grafted silicas were
subsequently evaluated in propanoic (C3), hexanoic (C6), lauric
(C12), and palmitic (C16) acid esterication with methanol at
60 C to assess the interplay between catalyst pore diameter,
pore architecture, and organic acid chain length on activity
(Supporting Information, Figures S5S9). Representative
reaction proles for the PrSO3H-KIT-6-80 and PrSO3H-KIT6-120 samples, possessing 5.2 and 7.0 nm pores, are shown in
Figure 6. Although both catalysts show slower initial rates and
lower conversions with increasing acid chain length, the relative
drop in performance of the larger pore PrSO3H-KIT-6-120 is
slight compared with that of PrSO3H-KIT-6-80 which is very
poor for lauric and palmitic acid. This suggests that signicant
mass-transport limitations can be important for relatively small
fatty acids (>C6), even when relatively large (5 nm) porous
catalysts are employed. However, slight pore-expansion can
prove sucient to alleviate these diusional eects.
A general decrease in esterication rate with alkyl chain
length is of course expected, and previously reported in C2C8
acid esterication using both H2SO4 and silica/Naon
composite SAC-13.45 Such decreases are attributed to a
combination of polar and steric inuences of the alpha
substituent on the carboxylic group. Inductive eects may
decrease reactivity; while the carboxylate electron density
increases with alkyl chain length, favoring initial protonation,
the electrophilicity of the carbonyl simultaneously decreases,
thus disfavoring subsequent alkoxy insertion.45 Above C4 chain
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Figure 4. TEM images of parent and sulfonated KIT-6 silicas; (a) KIT-6-80, (b) PrSO3H-KIT-6-80, (c) KIT-6-100, (d) PrSO3H-KIT-6-100, (e)
KIT-6-120, (f) PrSO3H-KIT-6-120.

Table 2. Surface and Bulk Properties of KIT-6 and SBA-15 Sulphonic Acid Silicas
catalyst

surface
areaa/
m2 g1

BJH pore
diameterb/
nm

plane
spacing/
nm

unit cell
parameter/
nm

wall
thickness/
nm

bulk S
contentc/
wt %

surface S
contentd/
wt %

acid site
loadinge/
mmol g1

acid site
density/H+
nm2

PrSO3H-KIT-6-80
PrSO3H-KIT-6-100
PrSO3H-KIT-6-120
PrSO3H-SBA-1580

540
539
546
813

5.2
6.2
7.0
4.9

8.6
9.4
9.5
9.2

21.1
23.0
23.3
10.6

5.3
5.3
4.7
6.1

0.74
0.73
0.72
1.12

0.66
0.73
0.69
0.95

0.32
0.25
0.38
0.67

0.35
0.28
0.42
0.49

From BET equation. bAnalyzed from the desorption branch. cBulk S content from TGA (weight loss between 450600 C). dSurface S content
from XPS. eBased on NH3 chemisorption (accurate to 0.05 mmolg1).

5 nm architectures. Pore expansion mitigates this problem, with


PrSO3H-KIT-6-100 and PrSO3H-KIT-6-120 exhibiting a
monotonic improvement over PrSO3H-SBA-15 with increasing
alkyl chain length, conferring a 2-fold rate enhancement for
palmitic acid esterication. Table 3 compares palmitic acid
esterication TOFs over dierent sulfonic acid silicas, and
demonstrates that our new PrSO3H-KIT-6 solid acid catalysts

esterication also verify the stability of the grafted acid sites on


both PrSO3H-SBA-15 and PrSO3H-KIT-6-120 under the mild
operating conditions employed in this study.
Figure 8 shows the relative performance of PrSO3H-KIT-6
catalysts versus PrSO3H-SBA-15. The enhanced performance of
PrSO3H-KIT-6-80, apparent for propanoic and hexanoic acids,
is lost >C6, consistent with limited in-pore accessibility for both
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Figure 5. S 2p XP spectra of propyl sulfonic acid derivatized SBA-15


and KIT-6 catalysts (tted spinorbit doublet shown as dotted lines).

Figure 7. Comparative performance of PrSO3H-SBA-15 and PrSO3HKIT-6 series versus Amberlyst 15 in propanoic, hexanoic, lauric, and
palmitic acid esterication with methanol at 60 C.

Figure 8. Relative performance of PrSO3H-KIT-6 versus PrSO3HSBA-15 in fatty acid esterication with methanol at 60 C as a function
of acid chain length.
Figure 6. Reaction proles for () propanoic, () hexanoic, ()
lauric, and () palmitic acid esterication with methanol at 60 C
over (a) PrSO3H-KIT-6-120 and (b) PrSO3H-KIT-6-80.

SBA-15 crystal or a 8.4 8.4 8.4 m KIT-6 crystal, assuming


1 pore per face of the SBA-15 unit cell and 4 pores per face of
the KIT-6 unit cell as shown in Scheme 1.] In contrast, the
three-dimensional nature of KIT-6 aords access to the interior
of crystallites via pore entrances uniformly distributed across
the entire external surface, providing far higher accessibility
(6400 pore entrances m3 for our KIT-6-80 crystallites),
which we believe contributes to the superior performance
observed in the present study. A consequence of these diering
pore architectures is that decreasing the length of pore channels
within SBA-15 crystallites can dramatically enhance the surface
density of pore openings (conned to the end faces) relative to
the crystallite volume, and thus accessibility of the porous
interior, resulting in signicant rate-enhancements as observed
for platelet-like SBA-15 with short (150350 nm) mesochannels toward fatty acid esterication.51 Mechanical grinding
of SBA-15 to reduce their pore channel length confers similar
catalytic promotion.52 We are currently undertaking molecular
dynamics simulations to better understand and optimize FFA

consistently outperform their PrSO3H-SBA-15 counterparts


possessing similar pore diameters, despite possessing similar
acid strengths. Since the TOF should be a constant if the
intrinsic reaction kinetics of a unique active site (e.g., a sulfonic
acid moiety) are measured, the observed variation in Table 3
suggests that other factors relating to the pore architecture play
an important role in regulating fatty acid esterication. SBA-15
crystallites exhibit a high aspect ratio of approximately 60 6
m (Supporting Information, Table S1, Figure S11) reecting
the many micrometer-length, parallel pore channels spanning
the longer axis. In such a morphology, pore entrances
preferentially dominate the smaller end faces, giving rise to a
net low number of openings averaged across the entire
crystallite volume (290 pore entrances.m3 for the crystallite
dimensions in this study). [Calculated for a 61 6.5 6.5 m
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ACS Catalysis

Research Article

Funding

Table 3. Palmitic Acid Conversion and Turnover


Frequencies (TOFs) for KIT-6 and SBA-15 Sulfonic Acid
Silica

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Publication Date (Web): July 9, 2012 | doi: 10.1021/cs300161a

catalyst

pore
diameter
/nm

acid
conv.a
/%

TOFb
/h1

TOFc
/h1

Amberlyst-15

na

45.0

3.6

na

PrSO3H-SBA-15

4.9

35.6

19.7

34.1

PrSO3H-KIT-6-80

5.2

13.6

21.0

33.2

PrSO3H-KIT-6-100

6.2

27.6

41.0

41

PrSO3H-KIT-6-120

7.0

39.3

50.9

60.7

PrSO3H-SBA-15-6
PrSO3H-SBA-15-8
PrSO3H-MM-SBA-15-4

6
8
4/300d

23.2
32.9
55.4

na
na
na

23.4
55.2
35.6

We thank the EPSRC for funding (EP/F063423/2). K.W.


acknowledges The Royal Society for the award of an Industry
Fellowship, and A.F.L. thanks the EPSRC for the award of a
Leadership Fellowship (EP/G007594/2).

reference

Notes

The authors declare no competing nancial interest.

this
work
this
work
this
work
this
work
this
work
33
33
32

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Conversion after 6 h reaction. bTOF based on NH3 titration.


Calculated per S site (based on bulk S content obtained by TGA).
d
Bimodal macro-mesoporous hierarchical pore structure.
c

diusion via tuning the relative mesopore channel length,


diameter, and interconnectivity. Future work will also explore
the impact of cografted hydrophobic groups, the use of stronger
acid functionalities (e.g., phenyl sulfonic acid), and means to
increase acid site loadings and overall yields in fatty acid
esterication employing these interconnected catalyst support
architectures.

4. CONCLUSIONS
The rst pore-expanded KIT-6 sulfonic acid catalysts have been
synthesized and applied to the esterication of fatty acids with
methanol. PrSO3H-KIT-6 hydrothermally aged at 80 C
exhibits strong TOF-enhancements in propanoic and hexanoic
acid esterication over a SBA-15 sulfonic acid of similar pore
diameter. This is attributed to improved mass transport arising
via the interconnected pore network of small KIT-6 cubic
crystallites, compared to the two-dimensional, non-interconnected pores of larger, elongated SBA-15 crystallites, and
associated enhanced access to the active sulfonic acid sites. Pore
accessibility becomes rate-limiting for lauric and palmitic acid
esterication for 5 nm KIT-6 and SBA-15 frameworks;
however, hydrothermal aging at 120 C facilitates KIT-6 pore
expansion up to 7 nm, enhancing esterication activity toward
all C3C16 fatty acids over PrSO3H-SBA-15, oering a 2-fold
TOF-enhancement for lauric and palmitic acid esterication.

ASSOCIATED CONTENT

* Supporting Information
S

Porosimetry of sulfonic acid catalysts, reaction proles used to


determine catalyst activity for the series of organic acids and
leaching studies. This material is available free of charge via the
Internet at http://pubs.acs.org.

REFERENCES

AUTHOR INFORMATION

Corresponding Author

*E-mail: Wilsonk5@cardi.ac.uk..
Present Address

UCCS, University of Lille I, 59655 Villeneuve dAscq, Lille,


France.
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